Cleaning and sanitizing concentrate containing lemon-lime fragrance

ABSTRACT

THIS INVENTION IS BASED UPON THE DISCOVERY THAT A SUBLIMINIAL QUANTITY OF A LEMON-LIME FRAGRANCE CAN BE EMPLOYED EFFECTIVELY WITHOUT DEGRADATION IN A LIQUID, LOW PH, SANITIZING AND CLEANING SOLUTION CONTAINING QUATERNARY AMMONIUM HALIDES TO PRODUCE A FRESH, CLEAN FRAGRANCE SENSATION WITHOUT PRODUCING AN AWARENESS OF THE SPECIFIC LEMON-LIME ODOR. A CLEANING AND SANITIZING CONCENTRATE IS DISCLOSED CONSISTING ESSENTIALLY OF (A) PHOSPHORIC OR HYDROXYACETIC ACID, (B) A NONIONIC SYNTHETIC DETERGENT,   (C) A QUATERNARY AMMONIUM HALIDE, (D) WATER, AND (E) LEMON-LIME FRAGRANCE.

CLEAN ODOR PREFERENCE May 15, 1973 3,733,277

R. P. WOODEN ET AL CLEANING AND SANITIZING CONCENTRATE CONTAININGLEMON-LIME FRAGRANCE Filed Dec. 6, i971 FRAGRANCE AS PER CENT OFQUATERNARY CPD.

United States Patent Oflice 3,733,277 Patented May 15, 1973 US. Cl.252-106 8 Claims ABSTRACT OF THE DISCLOSURE This invention is based uponthe discovery that a subliminal quantity of a lemon-lime fragrance canbe employed effectively without degradation in a liquid, low pH,sanitizing and cleaning solution containing quaternary ammonium halidesto produce a fresh, clean fragrance sensation without producing anawareness of the specific lemon-lime odor. A cleaning and sanitizingconcentrate is disclosed consisting essentially of (a) phosphoric orhydroxyacetic acid, (b) a nonionic synthetic detergent, (c) a quaternaryammonium halide, (d) water, and (e) lemon-lime fragrance.

CROSS REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of applicants copending application, Ser. No.887,529, filed Dec. 25, 1969, and now abandoned, entitled Fragrance forSanitizing and Cleaning Solutions.

BACKGROUND OF THE INVENTION A fragrance or perfume is used inconjunction with many cleaning and sanitizing solutions now beingmarketed. However, these fragrances are often damaged or incompatiblewith certain components of these solutions such as acids and quaternaryammonium halide sanitizers. Even if the fragrance is not degraded bythese components, the fragrance will generally produce the specific odorcharacteristics of that fragrance in the room that is cleaned.

In contrast to the prior art, this invention has the following objects:

(a) The provision of an improved sanitizing and cleaning solutiontogether with a specific amount of a lemonlime fragrance adapted toproduce a clean, fresh odor without imparting a distinguishablelemon-lime aroma of is own; and,

(b) The provision of a cleaner containing a suitable nonionic detergent,phosphoric acid or hydroxyacetic acid, a quaternary ammonium halidesanitizer and a subliminal amount of a lemon-lime fragrance adapted toproduce a clean, fresh odor in a freshly cleaned room in which thefragrance Will not be damaged or otherwise deodorized by the sanitizer.

SUMMARY OF THE INVENTION The product of this invention is a cleaning andsanitizing concentrate comprising, by weight, from to 50% phosphoric orhydroxyacetic acid; from 5% to nonionic detergent; from 10% toquaternary ammonium halides having the following formula:

wherein R and R are ethyl or methyl and R is an alkyl chain containingfrom 6 to 20 carbon atoms, n equals 0, 1 or 2, and X is selected fromthe group consisting of chloride ion, bromide ion and iodide ion; from15% to 65% water; and from 0.5 to 2 parts lemon-lime fragrance for eachparts by weight of quaternary ammonium halide. The lemon-lime fragranceis used is such amounts that when the concentrate is diluted with from250 to 1500 parts water per part of concentrate, a clean, freshfragrance is provided in a freshly cleaned room without producing aperceptible lemon-lime fragrance.

DESCRIPTION OF THE DRAWING The drawing is a graph of preference versuslemon-lime fragrance as a percentage of the quaternary ammonium halideand demonstrates the critical amount of lemonlime fragrance requiredherein.

DESCRIPTION OF THE PREFERRED EMBODIMENT Briefly, the present inventionis based upon the discovery that a subliminal quantity of a lemon-limefragrance can be employed effectively in a sanitizing and cleaningsolution to produce fresh, clean fragrance sensation proximate cleanedsurfaces without producing a perceptible lemon-lime odor or fragrance.

In a preferred aspect of this invention, the cleaning and sanitizingcomposition is first manufactured in concentrate form and subsequentlydiluted with water by the ultimate user. The concentrate, as describedhereinafter, is preferably diluted with from 250 parts to 1500 partswater per part of concentrate. The amount of Water used in diluting theconcentrate is specifically related to the desired cleaning function.For cleaning bathroom bowls, shower tile, etc., a relatively smallamount of water is used to dilute the concentrate. For less stringentcleaning, e.g., cleaning mirrors and less soiled hard surfaces, morewater is used to dilute the concentrate. The concentrate will bespecifically described in the following paragraphs.

From 20% to 50% of the concentrate is comprised of phosphoric orhydroxyacetic acid. Both of these acids are sufiiciently strong toprovide a concentrate pH ranging from about 0.3 to 0.75 and a usedilution pH of 0.5 to 2.0. Both of these acids are compatible with thequaternary ammonium halides and nonionic detergents used herein. Theacids are utilized in this formula to remove mineral deposits, e.g.,carbonates, stearates, blood stains, iron salts and water spots.

Nonionic synthetic detergents comprise from 5% to 25%, preferably from10% to 20%, of the concentrate. Nonionic synthetic detergents can bebroadly defined as compounds produced by the condensation of alkylenoxide groups (hydrophilic in nature with an organic hydrophobiccompound, which may be aliphatic or alkyl aromatic in nature. The lengthof the hydrophilic or polyoxyalkylene radical which is condensed withany particular hydrophobic groups can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements. The following nonionic syntheticdetergents can be successfully used herein:

(1) The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the ethylene oxide beingpresent in amounts equal to 5 to 25 moles of ethylene oxide per mole ofalkyl phenol. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, diisobutylene, octene, or nonene, forexample. One suitable member of this class is octyl phenoxy polyethoxyethanol wherein 7 to 8 moles of ethylene oxide are condensed with onemole of octyl phenol. This compound is a water-soluble liquid withexcellent wetting and detergent properties. It is a clear, pale,straw-colored liquid with a mild odor typical of detergents. It iscompatible with low pH systems and with quaternary ammonium compounds.

(2) The condensation product of aliphatic alcohols having from 8 to 22carbon atoms, in either straight chain or branched chain configuration,with ethylene oxide, for example, a coconut alcohol-ethylene oxidecondensate having from to 30 moles of ethylene oxide per mole of coconutalcohol, the coconut alcohol fraction having from to 14 carbon atoms.

(3) The condensation product of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol. Thehydrophobic portion of the molecule, which exhibits water in solubilityhas a molecular weight of from about 1500 to 1800. The liquid characterof this product is retained up to the point where the ethylene oxidecontent is about 50% of the total weight of the condensation product.

(4) Those nonionic synthetic detergents derived from the condensation ofethylene oxide with the product resulting from the reaction of propyleneoxide and ethylene diamine. For example, compounds containing from about40% to about 80% ethylene oxide by weight and having a molecular weightof from about 5,000 to about 11,000 resulting from the reaction ofethylene oxide groups with a hydrophobic base constituted of thereaction product of ethylene diamine and excess propylene oxide, saidbase having a molecular weight of the order of 2500 to 3000, aresatisfactory. The nonionics are used herein primarily for theirdetergency effects.

From 10 to 30%, preferably to of the concentrate is comprised ofquaternary ammonium halides having the following formula:

wherein R and R are ethyl or methyl and R is an alkyl chain containingfrom 6 to 20 carbon atoms, 12 equals 0, 1 or 2, and X is selected fromthe group consisting of chloride ions, bromide ions and iodide ions. Thequaternary ammonium halide is utilized in this concentrate because ofits excellent bactericidal activity. Specially preferred for use hereinis a mixture of quaternary ammonium halides containing n-alkyl C14 30%C16, 5% C and 5% C dimethyl benzyl ammonium chlorine and 50% n-alkyl(50% C 30% C 17% C and 3% C dimethyl ethylbenzyl ammonium chloride.

In manufacturing quaternary ammonium halides, a significant amount ofwater is introduced into the quaternary product. Generally, the productcomprises about 50% active and 50% water. Herein, the total weight ofthe product including the active and the Water is used in computing theamount of fragrance to be added and the relative weight of the variousother components.

From 15% to of the concentrate is comprised of Water. This water, inaddition to that added with the quaternary ammonium halide, is requiredto adequately solubilize the nonionic and to prevent precipitation ofcomponents prior to dilution by the ultimate consumer. The upper limitof 65% is not critical but only represents a practical limit from atransportation standpoint.

Because the quaternary ammonium halides are particularly good biologicaldeodorizers, it was necessary to find a fragrance that would not bedeodon'zed or otherwise degraded by them while at the same timeproviding a clean, fresh fragrance in a cleaned room without adding anidentifiable odor of its own. It was discovered that this could beaccomplished by using a lemon-lime fragrance including both natural andartificial fragrances. While the composition of the lemon-lime fragrancemay be varied considerably, it generally includes most of the followingand preferably all of the following components: terpineol, linalool,aldehyde C aldehyde C geranyl acetate, citral, oil of lemon (coldpressed), cymene, dipentene, oil of lime (distilled), citronellol, amylcinnamic aldehyde, oil of jasmin, methyl anthranilate, yara yara,indole, cinnamic alcohol, linalyl acetate, benzyl butyrate, benzylacetate, citronellyl acetate and orange terpenes.

A typical formulation for lemon-lime of the type used in accordance withthe invention is the following:

TABLE I Component: Parts by weight Terpineol 1.00 Linalool 1.00 AldehydeC10 tAldehyde C 1.25 Geranyl acetate 1.75 Citral 60.00 Oil of lemon(cold pressed) 100.00 Cymene .10 Dipentene .10 Oil of lime (distilled).30 Citronellol .25 Amyl cinnamic aldehyde .35 Oil of jasmin .80 Methylanthraniliate .50 Yara yara .50 Indole .50 Cinnamic alcohol 2.00 Linalylacetate .05 Benzyl butyrate .05 Benzyl acetate .05 Citronellyl acetate.06 Orange terpenes 828.14

The amount of lemon-lime fragrance is critical as can be seen byreference to the drawing which illustrates the responses of a panel ofeight persons. Scores run from 1 to 4 with higher numbers indicatingincreased preference.

The tests used in constructing the curve shown in the figure wereperformed as follows. Cleaning solutions comprising phosphoric acid, anonionic synthetic detergent, a quaternary ammonium chloride sanitizer,water (in amounts specified hereinbefore) and various concentrations oflemon-lime fragrance were used for cleaning a bathroom in the usedilutions hereinbefore specified. The curve represents a preference forthe clean smell left in the room after the cleaner was used.Specifically, it was discovered that the preferred fragranceconcentration of the lemon-lime composition must be between aboutone-half and 2% of the amount of quaternary ammonium halide (50% active,50% water) used to produce the desired result when used in use dilutionsranging from 250 parts water per part of concentrate to 1500 parts waterper part of concentrate. When the concentration of fragrance wasincreased beyond about 2%, as above specified, the fragrance oflemon-lime gradually became discernible in the above use dilution. Theinvention is therefore the provision of a sanitizing and cleaningsolution which provides a fresh, clean smell in a freshly cleaned roomby utilizing a subliminal quantity of a lemon-lime fragrance. Thepreferred amount of fragrance is between about one-half and 2% by weightof the total quaternary ammonium halide (50% active, 50% water) present.

The concentrate form, above described, is the preferred embodiment ofthis invention. The concentrate can be readily shipped at low cost andthe ultimate consumer can add the bulkiest ingredient, water. Bysupplying the cleaning and sanitizing product in concentrate form, theultimate consumer can also tailor the product for specific jobs byincreasing or decreasing the use dilution.

The following example is illustrative of the present invention:

EXAMPLE I A cleaning and sanitizing concentrate was prepared from 40parts phosphoric acid, 20 parts of a mixture of quaternary ammoniumchlorides comprising 50% n-alkyl 5 (60% C 30% C 5% C 5% C dimethylbenzyl ammonium chloride and 50 n-alkyl (50% C 30% C 17% C 3% C dimethylethylbenzyl ammonium chloride, 10 parts octyl phenoxy polyethoxy ethanoland 29.7 parts water. The concentrate was divided into 9 aliquots and toeach aliquot was added 0.033 part of the fragrances listed below (0.033parts fragrance divided by 2.22 parts quaternary equals 1.5 partsfragrance per 100 parts quaternary):

Aliquot 1 Fritzsche D&O Inc. No. 42149 (Lemon-Lime) Aliquot 2 FritzscheD&O Inc. No. 41994 (Pine) Aliquot 3 Fritzsche D&O No. 42249 (Pine)Aliquot 4 (Fritzsche D&O Inc. No. 47314 (Woody Amber) Aliquot 5Fritzsche D&O Inc. No. 41985 (Musk) Aliquot 6 Fritzsche D& Inc. No.54566 (Woody Amber) Aliquot 7 Fritzsche D&O Inc. No. 43798 (Musk)Aliquot 8 Fritzsche D&O Inc. No. 49745 (Orange) Aliquot 9 Fritzsche D&OInc. No. 42193 (Orange) Bathroom testing was simulated by diluting eachconcentrate with 250 parts water per part of concentrate. One ml. of thediluted concentrate was placed in a 500 ml. jar. After about 15 minutes,fragrance experts odor tested these fragrances and found no degradationin the fragrance of aliquots 1, 8 and 9 and significant degradation inaliquots 2 through 7.

After 12 hours, the fragrance of aliquots 2 through 7 and 9 hadsignificantly degraded and were not desirable odors for this product.Concentrate 8 had a sweet, heavy orange odor which was unpleasant in thecontext of a bathroom.

The lemon-lime fragrance in aliquot 1 above did not degrade over a30-day period. When used in the manner described above, a clean, freshodor sensation was recognizable with no noticeable lemon-lime fragrance.This product, diluted as stated above, was used to clean a bathroom andleft a clean, fresh odor sensation in the bathroom with no noticeablelemon-lime fragrance.

What is claimed is:

1. A cleaning and sanitizing concentrate consisting essentially of:

(a) from 20% to 50% of an acid selected from the group consisting ofphosphoric and hydroxyacetic acid;

(b) from to 25% of a nonionic synthetic detergent;

(c) from 10% to 30% of quaternary ammonium halide having the followingformula:

wherein R and R are ethyl or methyl and R is an alkyl chain containingfrom 6 to 20 carbon atoms, n equals 0, 1 or 2, and X is selected fromthe group consisting of chloride ion, bromide ion and iodide ion;

(d) at least 15% water; and,

(e) from 0.5 parts to 2 parts lemon-lime fragrance for each parts byweight of said quaternary ammonium halide.

2. The cleaning and sensitizing concentrate of claim 1 wherein the pH ofsaid composition is between 0.3 and 0.75.

3. The cleaning and sanitizing concentrate of claim 2 wherein thenonionic synthetic detergent comprises from 10% to 20% of thecomposition.

4. The cleaning and sanitizing concentrate of claim 3 wherein theconcentrate contains from 20% to 30% of said quaternary ammonium halide.

5. The cleaning and sanitizing concentrate of claim 4 wherein thequaternary ammonium halide salt is a chloride salt.

6. The cleaning and sanitizing concentrate of claim 4 wherein thenonionic synthetic detergent is octyl phenoxy polyethoxy ethanol.

7. The cleaning and sanitizing concentrate of claim 4 wherein thequaternary ammonium halide is a mixture of n-alkyl C14, C16, C12, 5%C13) d] methyl benzyl ammonium chloride and 50% n-alkyl (50% C12, 30% C17% C 3% C dimethyl ethylbenzyl ammonium chloride.

8. The cleaning and sanitizing concentrate of claim 4 wherein the acidis phosphoric acid.

References Cited UNITED STATES PATENTS 2,702,774 2/ 1955 Stayner 252-l06X 2,998,390 8/1961 Hamilton 252106 X 3,223,643 12/1965 Law 252-1063,373,208 3/ 1968 -Blumenthal 252-522 X 3,382,285 5/1968 Egan et a1252--- X RICHARD D. LOVERIN G, Primary Examiner US. Cl. X.R.

252-136, 522, DIG. 1, DIG. 10, DIG. 14

